Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/40—Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/32—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising halogenated hydrocarbons as the major constituent
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent

Definitions

• the present invention relates to acrylic synthetic fibers having an animal hair-like touch and to its method for production, and more particularly relates to acrylic synthetic fibers having an animal hair-like touch and lustre and, moreover, having a proper elongation and an easily tractable property in the finishing treatment of the fiber and to the method of production of the fiber, which is characterized in spinning a solution of an acrylic copolymer dissolved in an organic solvent, further containing one or more kinds of metallic compounds and cellulose derivatives.
• Acrylic synthetic fibers have been hitherto considered to be fibers having a touch most similar to animal hair among many kinds of synthetic fibers from the standpoint of touch of fiber and easy treatment for fiber finishing and, accordingly, has been wisely applied in the field of imitation fur such as boa, seal and high pile modeled to animal fur.
• the acrylic synthetic fiber is compared with the natural hair, it has a disadvantage on the wet and soft feeling which is the special or characteristic feeling of the natural hair.
• post-treatment with a suitable treating agent has been utilized to date, however, the improvement has not yet been desirably obtained, since the treating agent gives a sticky feeling to the treated acrylic fibers.
• the effect of such a post-treatment has no durability to washing or drycleaning.
• the post-treatment with such a treating agent has a bad effect on the spinning process of the treated acrylic fiber, since the separating property of fiber is decreased.
• the present inventors have made an extensive study and found that it is possible to obtain superior acrylic synthetic fibers having a nice touch and lustre with a similarity to animal hair which has not been previously anticipated and, moreover, having a proper elongation and an easy tractable property in the finishing treatment of fiber, by the spinning of a solution of an acrylic copolymer dissolved in an organic solvent, further containing one or more kinds of chosen metallic compounds and cellulose derivatives, and thus the present invention has been completed.
• the copolymer used in the present invention consists of 30 weight % or more of acrylonitrile, 70 weight % and less of vinyl chloride and/or vinylidene chloride and 0 to 10 weight % of other polymerizable vinyl monomers.
• those copolymers obtained from such monomeric mixtures which consist of 30 to 80 weight % of acrylonitrile, 70 to 20 weight % of vinyl chloride and/or vinylidene chloride and 0 to 10 weight % of other polymerizable vinyl monomers can be prepared to give superior acrylic synthetic fibers which are suitable for use as animal hair-like products, since they have a nice workability at a temperature easily retained for further finishing, have a proper elongation and a tractable property with a superior durability and, moreover, have a proper bending resistance very similar to animal hair.
• the content of the acrylonitrile component is less than 30 weight %, the dyeability of the obtained acrylic fibers decrease and the characteristic property of acrylic synthetic fibers of the acrylonotrile series
• the other polymerizable vinyl monomer mentioned above and used in the present invention include, for example, acrylic acid ester, methacrylic acid ester, acrylic amide, methacrylic amide or mono- and di-alkyl derivatives of the said amides, styrene or ⁇ and ⁇ -derivatives of styrene, vinyl acetate, vinyl pyrrolidone, vinyl pyridine or alkyl derivatives of vinyl pyridine, acrylic acid, methacrylic acid, itaconic acid, p-styrene sulphonic acid, allyl sulphonic acid, methallyl sulphonic acid, paramethacryloyloxybenzene sulphonic acid, methacryloyloxypropyl sulphonic acid and metallic salts or amine salts of those acids mentioned above.
• the above mentioned co-polymers can be obtained by conventional polymerization methods using a polymerization initiator generally used in polymerization such as peroxide compounds, azo-compounds or various kinds of redox systems.
• a spinning solution is prepared by dissolving the obtained polymer in an organic solvent such as acetone, acetonitrile, dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide and the like.
• a stabilizer which is effective to improve such properties as anti-yellow change, light-resisting property and anti-weathering property.
• Metallic compounds used in the present invention include silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), zirconium oxide (ZrO 2 ), aluminium oxide (Al.sub. 2 O 3 ), antimony oxide (Sb 2 O 3 ), magnesium oxide (MgO), calcium oxide (CaO), zinc oxide (ZnO), tin oxide (SnO), titanium hydroxide (Ti(OH) 4 ), zirconium hydroxide (ZrO(OH).sub. 2), aluminium hydroxide (Al(OH) 3 ), magnesium hydroxide (Mg(OH) 2 ), zinc hydroxide (Zn(OH) 2 ), aluminium phosphate (AlPO.sub.
• Cellulose derivatives used in the present invention include acetyl cellulose, acetyl propionyl cellulose, acetyl butyryl cellulose and the like.
• the degree of acylation such as acetylation, etc. in cellulose derivatives mentioned above is chosen in the region where the cellulose derivatives are soluble in the solvent used for the preparation of co-polymer dope solution.
• the degrees are as follows:
• acetyl cellulose the region of degree of acetylation is 37.0 to 43.2%
• acetyl propionyl cellulose the region of degree of acetylation is 2.5 to 15.0% and that of propionylation is 30.0 to 45.0%
• acetyl butyryl cellulose the region of degree of acetylation is 1.6 to 29.5% and that of butyrylation is 17.0 to 53.0%.
• At least one of the metallic compounds described above are used in an amount in the range of from 0.1 to 8.0 parts per 100 parts of copolymer, and, preferably, 0.5 to 6.0 parts. In cases where less than 0.1 parts are used, no effect by the addition of metallic compounds can be found and in the case where more than 8.0 parts of the metallic compounds are used, undesirable effects result as to the mechanical properties of the obtained acrylic synthetic fibers and, moreover, the spinning properties of the prepared polymer solution decrease.
• At least one kind of cellulose derivative is used in an amount in the range of from 1.0 to 8.0 parts per 100 parts of copolymer and, preferably, 2.0 to 6.0 parts.
• thickener examples include acrylic copolymer used in the present invention, homopolymers of glycidyl acrylate, glycidyl methacrylate, methyl acrylate or methyl methacrylate and copolymers of more than 30 weight % of glycidyl acrylate or glycidyl methacrylate and less than 80 weight % of other monomers which can co-polymerize with the said glycidyl acrylate or glycidyl methacrylate such as methylacrylate, methyl methacrylate, vinyl acetate, acrylonitrile, vinyl chloride, vinylidene chloride, acrylic amide and the like.
• the thickener After dissolving the thickener as mentioned above in an organic solvent such as acetone, acetonitrile, dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, etc. to prepare a solution whose viscosity is in a range of 5 to 1,000 cps and then adding metallic compounds of the present invention to the solution, the mixture is subjected to an agimixer, submicron, ball mill, vibration mill or sand grinder to obtain a stable and uniform dispersion.
• the uniformity of the dispersion solution provides stable spinning conditions for the spinning solution and, moreover, assists in obtaining desirable properties for the resulting acrylic fibers.
• the viscosity of the solution mentioned above was observed by using a viscometer of the VS type (manufactured by the Tokyo Measuring Instruments Co., Ltd.).
• the desirable or characteristic features of the present invention are primarily due to the combined effect on the acrylic fiber of the said metallic compound and cellulose derivative which co-exist in the spinning solution of co-polymer.
• Such desirable results are not obtained when either the metallic compound or cellulose derivative is used alone.
• the obtained acrylic synthetic fibers have the touch and lustre very similar to natural animal hair.
• the synthetic fiber thus obtained is scant of transparency and lustre in the inner structure of the fiber and the surface of the fiber becomes rough and hard but still has its lustre on the surface of the fiber.
• the cellulose derivative only is used, the decrease in lustre of the obtained synthetic fiber is scarcely noticed.
• a synthetic fiber having deep wrinkles along the longitudinal axis of the fiber on its surface and having a considerable decrease in lustre is obtained. This is due to the different coagulating behavior of the polymeric composition in solution under spinning conditions. This appears to be the case when producing the desired fibers of the present invention, when considering the visual and tactile properties.
• the second desirable or characteristic feature of the present invention is to be able to obtain an animal hair-like acrylic synthetic fiber, having a strong resistance to dry cleaning and washing and to retain its characteristic touch and appearance which is very similar to animal hair. It is to be emphasized that the desirable touch and appearance of the fibers of the present invention are not accomplished by a post-treatment of the surface of the fiber but are accomplished as the result of the synergistic effects of the two components, i.e., the metallic compound and cellulose derivative, which co-exist in the fiber itself.
• the dry cleaning was carried out, using perchlorethylene in the amount of 40 parts per one part of fabric, at 25° C for 30 minutes in a launder meter and the washing was carried out, using 5g/l of a washing agent and 40 parts of water per one part of fabric, at 40° C for 30 minutes in a domestic washing apparatus.
• a spinning solution (C-1) was prepared by dissolving into 400 parts of acetone 100 parts of a copolymer (whose specific viscosity of cyclohexanone solution containing 2.0g of the copolymer per liter of solution was 0.253 at 30° C) obtained from a monomeric mixture of 50 parts of acrylonitrile, 49 parts of vinyl chloride and 1 part of sodium p-styrene sulfonate.
• an acetone solution was prepared containing a copolymer (whose specific viscosity of acetone solution containing 8.0g/l of solution was 0.02 at 30° C) consisting of 15 parts of acrylonitrile and 85 parts of glycidyl acrylate. Then, 50 parts of this solution (whose viscosity was 140 cps) was mixed with 50 parts of metallic compounds chosen for use in this example and the mixture was admixed in a ball mill to prepare a stable suspension.
• a copolymer whose specific viscosity of acetone solution containing 8.0g/l of solution was 0.02 at 30° C
• 50 parts of this solution (whose viscosity was 140 cps) was mixed with 50 parts of metallic compounds chosen for use in this example and the mixture was admixed in a ball mill to prepare a stable suspension.
• a spinning solution (E-1) was prepared by dissolving into 400 parts of acetonitrile 100 parts of copolymer (whose specific viscosity of a dimethyl formamide solution containing 2.0g of polymer per liter of solution was 0.285 at 30° C) consisting of a mixture of 61 parts of acrylonitrile, 38.5 parts of vinyl chloride and 0.5 parts of sodium allyl sulfonate.
• a spinning solution (F-1) was prepared by dissolving into 400 parts of dimethyl formamide 100 parts of copolymer (whose specific viscosity of dimethyl formamide solution containing 2.0g of polymer per liter of solution was 0.311 at 30° C) consisting of a mixture of 75 parts of acrylonitrile, 24 parts of vinyliden chloride and 1 part of sodium p-styrene sulfonate.
• a spinning solution (G-1) was prepared by mixing into 100 parts of the copolymer spinning solution (A-1) of Example 1, 2 parts of zinc sulphide, 1 part of calcium sulphate and 3 parts of acetyl cellulose (having a degree of acetylation of 37.8%).
• a spinning solution (H-1) was prepared by adding 1.5 parts of zinc sulphide, 3.5 parts of barium sulphate and 4 parts of acetyl butyryl cellulose (having a degree of acetylation of 29.5% and butyrylation of 17%) into 100 parts of the copolymer spinning solution (B-1) prepared in Example 2.
• a spinning solution (J-1) was prepared, dissolving into 400 parts of acetone 100 parts of a copolymer (whose specific viscosity of cyclohexanone solution containing 2.0g of the copolymer per liter of solution was 0.253 at 30° C) consisting of a mixture of 51 parts of acrylonitrile, 46 parts of vinyl chloride and 3 parts of methyl methacrylate.
• a copolymer (whose specific viscosity of cyclohexanone solution containing 2.0g of the polymer per liter of solution was 0.253 at 30° C) consisting of 50 parts of acrylonitrile, 49 parts of vinyl chloride and 1 part of sodium p-styrene sulfonate was dissolved into dimethyl formamide and a polymer solution was prepared (whose viscosity was 300 cps). Then, 50 parts of this solution as prepared and 60 parts of metallic compounds chosen for use in the present example were mixed together and the mixture was admixed in a ball mill to make a stable suspension.
• a spinning solution (K-4) was prepared by adding 1 part of zirconium oxide and 1 part of zirconium hydroxide to 100 parts of the copolymer of the spinning solution (K-1).
• a spinning solution (L-1) was prepared by adding 2 parts of zinc sulphide and 6 parts of acetyl cellulose (having a degree of acetylation of 39.8%) to 100 parts of the copolymer contained in the spinning solution (K-1).
• a spinning solution (L-2) was prepared by adding 1.5 parts of zinc sulphide, 3.5 parts of barium sulphate, 3 parts of acetyl cellulose (having a degree of acetylation of 39.8%) and 3 parts of acetyl butyryl cellulose (having a degree of acetylation of 13% and butyrylation of 37%) to 100 parts of the copolymer contained in the spinning solution (K-1).
• a spinning solution (L-3) was prepared by adding 3 parts of aluminium phosphate, 0.5 parts of calcium phosphate, 1 part of an acetyl butyryl cellulose (having a degree of acetylation of 29.5% and butyrylation of 17%), 2 parts of an acetyl butyryl cellulose (having a degree of acetylation of 13% and butyrylation of 37%) and 3 parts of an acetyl butyryl cellulose (having a degree of acetylation of 6% and butyrylation of 48%) into 100 parts of the copolymer contained in the spinning solution (K-1).
• a spinning solution (L-4) was prepared by adding 2 parts of zinc sulphide, 1 part of calcium sulphate, 1 part of an acetyl cellulose (having a degree of acetylation of 37.8%) and 2 parts of an acetyl cellulose (having a degree of acetylation of 40.5%) into 100 parts of the copolymer contained in the spinning solution (K-1).

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Artificial Filaments (AREA)

Applications Claiming Priority (4)

Related Parent Applications (1)

Publications (1)

Family

ID=26365325

Family Applications (1)

Country Status (3)

Cited By (7)

Citations (7)

Family Cites Families (4)

• 1975
  • 1975-02-24 GB GB772075A patent/GB1460251A/en not_active Expired
  • 1975-03-05 DE DE2509633A patent/DE2509633C2/de not_active Expired
  • 1975-06-03 US US05/583,513 patent/US4012346A/en not_active Expired - Lifetime

Patent Citations (7)

Non-Patent Citations (1)

Also Published As

Similar Documents